WO2011146580A2 - Compositions durcissables - Google Patents

Compositions durcissables Download PDF

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Publication number
WO2011146580A2
WO2011146580A2 PCT/US2011/036945 US2011036945W WO2011146580A2 WO 2011146580 A2 WO2011146580 A2 WO 2011146580A2 US 2011036945 W US2011036945 W US 2011036945W WO 2011146580 A2 WO2011146580 A2 WO 2011146580A2
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WO
WIPO (PCT)
Prior art keywords
composition
dioxide
divinylarene dioxide
curable
divinylarene
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PCT/US2011/036945
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English (en)
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WO2011146580A3 (fr
WO2011146580A9 (fr
Inventor
Maurice J. Marks
Roy V. Snelgrove
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Dow Global Technologies Llc
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Application filed by Dow Global Technologies Llc filed Critical Dow Global Technologies Llc
Priority to MX2012013529A priority Critical patent/MX2012013529A/es
Priority to BR112012029587A priority patent/BR112012029587A2/pt
Priority to US13/696,814 priority patent/US20130059945A1/en
Priority to CN2011800251447A priority patent/CN102906148A/zh
Priority to RU2012155687/04A priority patent/RU2581832C2/ru
Priority to EP11721961A priority patent/EP2571918A2/fr
Priority to KR1020127033287A priority patent/KR20130090789A/ko
Priority to JP2013512081A priority patent/JP2013533901A/ja
Publication of WO2011146580A2 publication Critical patent/WO2011146580A2/fr
Publication of WO2011146580A3 publication Critical patent/WO2011146580A3/fr
Publication of WO2011146580A9 publication Critical patent/WO2011146580A9/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention is related to curable formulations or compositions including a stoichiometric excess of a divinylarene dioxide, a co-reactive curing agent, and a catalyst.
  • Divinylarene dioxides such as divinylbenzene dioxide (DVBDO) are known to be used in the epoxy resin matrix component in curable compositions for producing thermoset resin products.
  • divinylarene dioxides have been used in
  • stoichiometric amounts with amine, anhydride, or phenolic curing agents.
  • GB 854679 describes curable compositions of stoichiometric amounts of divinylbenzene dioxide and polyfunctional amines
  • GB 855025 describes curable compositions of stoichiometric amounts of divinylbenzene dioxide and carboxylic acid anhydrides
  • JP 2009119513 describes curable compositions of stoichiometric amounts of
  • divinylbenzene dioxide and polyphenols do not teach the advantages of using a stoichiometric excess of a divinylarene dioxide as the epoxide component in a curable composition.
  • WO 2008140906 Al describes curable compositions having an excess of epoxy resins and curing agents, but WO 2008140906 does not disclose the use of divinylarene dioxides as the epoxide resin component in a curable composition.
  • WO 2008140906 Al also does not describe the advantages of using a stoichiometric excess of a divinylarene dioxide as the epoxide component in a curable composition.
  • the prior known divinylarene dioxide-containing curable compositions have a lower than desired pot life and the resulting thermosets have a lower than desired heat resistance for many applications.
  • Curable divinylarene dioxide compositions having an improved pot life prior to cure and an improved heat resistance after cure are needed in many epoxy thermoset applications.
  • the present invention is directed to curable (also referred to as polymerizable or thermosettable) formulations or compositions having a stoichiometric excess of divinylarene dioxides and co-reactive curing agents such as amines, anhydrides, or polyphenols that have a longer pot life prior to cure and produce a thermoset or cured product having a higher heat resistance after cure compared to analogous prior art compositions made using stoichiometric compositions.
  • the curable compositions of the present invention are advantageously useful as thermoset materials, coatings, composites, and adhesives.
  • One broad embodiment of the present invention comprises a curable epoxy resin composition including (a) a stoichiometric excess of a divinylarene dioxide, (b) a co-reactive curing agent, and (c) a catalyst, wherein the composition exhibits a long pot life prior to curing the composition.
  • Another broad embodiment of the present invention comprises a curable epoxy resin composition including (a) a stoichiometric excess of a divinylarene dioxide, (b) a co-reactive curing agent, and (c) a catalyst to effect reaction of the excess epoxide;
  • the resultant cured composition provides a durable thermoset material.
  • the divinylarene dioxide, component (a), useful in the present invention may comprise, for example, any substituted or unsubstituted arene nucleus bearing one, two, or more vinyl groups in any ring position.
  • the arene portion of the divinylarene dioxide may consist of benzene, substituted benzenes, (substituted) ring-annulated benzenes or homologous ly bonded (substituted) benzenes, or mixtures thereof.
  • the divinylbenzene portion of the divinylarene dioxide may be ortho, meta, or para isomers or any mixture thereof.
  • Additional substituents may consist of H 2 0 2 -resistant groups including saturated alkyl, aryl, halogen, nitro, isocyanate, or RO- (where R may be a saturated alkyl or aryl).
  • Ring-annulated benzenes may consist of naphthlalene, tetrahydronaphthalene, and the like.
  • Homologously bonded (substituted) benzenes may consist of biphenyl, diphenylether, and the like.
  • the divinylarene dioxide used for preparing the composition of the present invention may be illustrated generally by general chemical Structures I-IV as follows:
  • each R 5 R 2 , R 3 and R 4 individually may be hydrogen, an alkyl, cycloalkyl, an aryl or an aralkyl group; or a H 2 0 2 -resistant group including for tple a halogen, a nitro, an isocyanate, or an RO group, wherein R may be an alkyl, aryl or aralkyl; x may be an integer of 0 to 4; y may be an integer greater than or equal to 2; x+y may be an integer less than or equal to 6; z may be an integer of 0 to 6; and z+y may be an integer less than or equal to 8; and Ar is an arene fragment including for example,
  • R4 can be a reactive group(s) including epoxide, isocyanate, or any reactive group and Z can be an integer from 0 to 6 depending on the substitution pattern.
  • the divinylarene dioxide used in the present invention may be produced, for example, by the process described in U.S. Patent Provisional
  • the divinylarene dioxide useful in the present invention may comprise, for example, divinylbenzene dioxide, divinylnaphthalene dioxide, divinylbiphenyl dioxide, divinyldiphenylether dioxide, and mixtures thereof.
  • the divinylarene dioxide used in the epoxy resin composition may be for example divinylbenzene dioxide (DVBDO).
  • the divinylarene dioxide component that is useful in the present invention includes, for example, a divinylbenzene dioxide as illustrated by the following chemical formula of Structure V:
  • the chemical formula of the above DVBDO compound of Structure V may be as follows: C1 0 H1 0 O2; the molecular weight of the DVBDO may be about 162.2; and the elemental analysis of the DVBDO may be about as follows: C, 74.06; H, 6.21; and O, 19.73 with an epoxide equivalent weight of about 81 g/mol.
  • Divinylarene dioxides particularly those derived from divinylbenzene such as for example DVBDO, are class of diepoxides which have a relatively low liquid viscosity but a higher rigidity and crosslink density than conventional epoxy resins.
  • the present invention includes a DVBDO illustrated by any one of the above Structures individually or as a mixture thereof.
  • Structures VI and VII above show the meta (1,3-DVBDO) and para isomers of DVBDO, respectively.
  • the ortho isomer is rare; and usually DVBDO is mostly produced generally in a range of from about 9: 1 to about 1 :9 ratio of meta (Structure VI) to para (Structure VII) isomers.
  • the present invention preferably includes as one embodiment a range of from about 6: 1 to about 1 :6 ratio of Structure VI to Structure VII, and in other embodiments the ratio of Structure VI to Structure VII may be from about 4: 1 to about 1:4 or from about 2: 1 to about 1:2.
  • the divinylarene dioxide may contain quantities (such as for example less than about 20 weight percent [wt ]) of ituted arenes.
  • the amount and structure of the substituted arenes depend on the process used in the preparation of the divinylarene precursor to the divinylarene dioxide.
  • divinylbenzene prepared by the dehydrogenation of diethylbenzene (DEB) may contain quantities of ethyl vinylbenzene (EVB) and DEB.
  • EVB ethyl vinylbenzene
  • EVB ethyl vinylbenzene
  • the divinylarene dioxide useful in the present invention comprises, for example, DVBDO, a low viscosity liquid epoxy resin.
  • the viscosity of the divinylarene dioxide used in the process of the present invention ranges generally from about 0.001 Pa s to about 0.1 Pa s, preferably from about 0.01 Pa s to about 0.05 Pa s, and more preferably from about 0.01 Pa s to about 0.025 Pa s, at 25 °C.
  • the utility of the divinylarene dioxides of the present invention requires thermal stability to allow formulating or processing the divinylarene dioxides at moderate temperatures (for example, at temperatures of from about 100 °C to about 200 °C) for up to several hours (for example, for at least 2 hours) without oligomerization or
  • the divinylarene dioxides of the present invention have sufficient thermal stability such that the divinylarene dioxides do not experience a substantial increase in viscosity or gelling during formulation or processing at the aforementioned moderate temperatures.
  • the rigidity property of the divinylarene dioxide is measured by a calculated number of rotational degrees of freedom of the dioxide excluding side chains using the method of Bicerano described in Prediction of Polymer Properties, Dekker, New York, 1993.
  • the rigidity of the divinylarene dioxide used in the present invention may range generally from about 6 to about 10, preferably from about 6 to about 9, and more preferably from about 6 to about 8 rotational degrees of freedom.
  • the concentration of the divinylbenzene dioxide in the composition of the present invention will include a stoichiometric excess.
  • the stoichiometric excess of divinylarene dioxides used is determined using the number of epoxide equivalents or the ?er of moles depending on the class of co-reactive curing agent used, as described below.
  • the concentration of the divinylarene oxide used in the present invention as component (a) of the composition may range in terms of equivalent ratio of epoxide to co-reactive curing agent generally from about 1.05 to about 10 in one embodiment, from about 1.05 to about 7 in another embodiment, from about 1.05 to about 5 in still another embodiment, and from about 1.05 to about 3 in yet another embodiment.
  • divinylbenzene dioxide as component (a) may be used in terms of equivalent ratio of epoxide to co-reactive curing agent from about 1.1 to about 2.
  • divinylarene dioxide in amounts greater than that listed above result in compositions having insignificant concentrations of co-reactive curing agent and thereby have properties which are essentially the same as divinylarene dioxide alone.
  • the co-reactive curing agent, component (b), useful for the curable epoxy resin composition of the present invention may comprise any conventional co-reactive curing agent known in the art for curing epoxy resins.
  • the curing agents, (also referred to as a hardener or cross-linking agent) useful in the curable composition may be selected, for example, from those curing agents well known in the art including, but are not limited to, anhydrides, carboxylic acids, amine compounds, phenolic compounds, thiols, or mixtures thereof.
  • co-reactive curing agents useful in the present invention may include any of the co-reactive curing materials known to be useful for curing epoxy resin based compositions.
  • co-reactive curing agents include, for example, polyamine, polyamide, polyaminoamide, dicyandiamide, polyphenol, polymeric thiol, polycarboxylic acid and anhydride, and any combination thereof or the like.
  • Other specific examples of co-reactive curing agent include phenol novolacs, bisphenol-A novolacs, phenol novolac of dicyclopentadiene, cresol novolac, diaminodiphenylsulfone, styrene-maleic acid anhydride (SMA) copolymers; and any combination thereof.
  • SMA styrene-maleic acid anhydride
  • amines and amino or amido containing resins and phenolics are preferred.
  • the curable resin compositions of the present invention can be cured using various standard co-reactive curing agents including for example amines, carboxylic acid anhydride, polyphenols, and mixtures thereof.
  • the amine curing agent may comprise any substituted or unsubstituted polyamine such as an ethylene amine exemplified by ethylenediamine, diethylenetriamine, triethylenetetramine, and aminoethylpiperazine; a cycloaliphatic amine such a
  • isophoronediamine a benzylic amine such as xylylene diamine; an aromatic amine such as methylenedianiline and diethyltoluenediamine; and mixtures thereof.
  • Stoichiometric excess of divinylarene dioxides is determined using the number of epoxide equivalents relative to the number of amine hydrogen equivalents of the amine curing agent.
  • the carboxylic acid anhydride curing agent may comprise any substituted or unsubstituted anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride and mixtures thereof. Stoichiometric excess of divinylarene dioxides is determined using the number of moles of divinylarene dioxide relative to the number of moles of anhydride curing agent.
  • the polyphenol curing agent may comprise any substituted or unsubstituted polyphenol such as a phenol novolac resin, a cresol novolac resin, and a bisphenol A novolac resin, a multi-phenolic compound such as cyclohexanetetraphenol, and a phenolic hardener such as D.E.H. 80 phenolic resin, and optionally including a diphenol such as bisphenol A, and also optionally including a monophenol such as p-t-butylphenol.
  • a substituted or unsubstituted polyphenol such as a phenol novolac resin, a cresol novolac resin, and a bisphenol A novolac resin
  • a multi-phenolic compound such as cyclohexanetetraphenol
  • a phenolic hardener such as D.E.H. 80 phenolic resin
  • a diphenol such as bisphenol A
  • a monophenol such as p-t-butylphenol
  • Stoichiometric excess of divinylarene dioxides is determined using the number of epoxide equivalents relative to the number of phenolic equivalents of the polyphenol curing agent.
  • Dicyandiamide may be one preferred embodiment of the curing agent useful in the present invention.
  • Dicyandiamide has the advantage of providing delayed curing since dicyandiamide requires relatively high temperatures for activating its curing properties; and thus, dicyandiamide can be added to an epoxy resin and stored at room temperature (about 25°C).
  • the thiol curing agent may comprise any substituted or unsubstituted polysulfide or polymercaptan compound.
  • Specific examples of the compounds useful as the g agent include the Thiokol LP series of polyalkylether thiols produced by Toray Fine Chemicals Co., Ltd. and Capcure LOF polymercaptan from Cognis Corp.
  • the catalyst, component (c), useful for the curable epoxy resin composition of the present invention may comprise any conventional catalyst known in the art for effecting the reaction between a curing agent and an epoxy resin.
  • the catalysts, useful in the curable composition may be selected, for example, from those catalysts well known in the art including, but are not limited to, tertiary amines, imidazoles, quaternary ammonium salts, quaternary phosphonium salts, Lewis acid-Lewis base complexes, or mixtures thereof.
  • the catalysts useful in the present invention include for example, a tertiary amine such as benzyldimethylamine; an imidazole such as
  • l-benzyl-2-methylimidazole a quaternary ammonium salt such as tetrabutylammonium bromide; a phosphonium salt such as tetrabutylphosphonium bromide; Lewis acid-Lewis base complexes such as boron trichloride-ethylamine complex; and mixtures thereof.
  • the epoxy resin composition of the present invention may include from about 0.01 wt % to about 20 wt % the catalyst. In other embodiments, the
  • composition may include from about 0.05 wt % to about 15 wt % catalyst; from about 0.1 wt % to about 10 wt % catalyst in other embodiments; from about 0.2 wt % to about 7 wt % catalyst in other embodiments; and from about 0.5 wt % to about 5 wt % catalyst in yet other embodiments.
  • an optional solvent may be used in preparing the curable divinylarene dioxide resin composition of the present invention.
  • one or more organic solvents well known in the art may include aromatic hydrocarbons, alkyl halides, ketones, alcohols, ethers, and mixtures thereof.
  • the concentration of the solvent used in the present invention may range generally from 0 wt % to about 95 wt %, preferably from about 0.01 wt % to about t ; more preferably from about 0.01 wt % to about 60 wt ; and most preferably from about 0.01 wt % to about 50 wt %.
  • the optional components may comprise compounds that can be added to the composition to enhance application properties (e.g. surface tension modifiers or flow aids), reliability properties (e.g. adhesion promoters) the reaction rate, the selectivity of the reaction, and/or the catalyst lifetime.
  • application properties e.g. surface tension modifiers or flow aids
  • reliability properties e.g. adhesion promoters
  • An assortment of optional additives that may be added to the curable compositions of the present invention include for example, other resins such as epoxy resins that are different from the divinylarene dioxide, component (a); diluents; stabilizers; fillers; plasticizers; catalyst de-activators; and the like; and mixtures thereof.
  • other resins such as epoxy resins that are different from the divinylarene dioxide, component (a); diluents; stabilizers; fillers; plasticizers; catalyst de-activators; and the like; and mixtures thereof.
  • additives useful in the composition of the present invention include for example fillers such as clay, talc, silica, and calcium carbonate; solvents such as ethers and alcohols; toughening agents such as elastomers and liquid block copolymers; pigments such as carbon black and iron oxide; surfactants such as silicones; fibers such as fiberglass and carbon fiber; and mixtures thereof.
  • the concentration of the optional components useful in the composition of the present invention may range generally from 0 wt % to about 99.9 wt %, preferably from about 0.001 wt % to about 99 wt %, more preferably from about 0.01 wt % to about 98 wt %, and most preferably from about 0.05 wt % to about 95 wt %.
  • the preparation of the curable divinylarene dioxide resin composition of the present invention is achieved by admixing (a) an excess of a stoichiometric amount of a divinylarene dioxide, (b) a co-reactive curing agent, and (c) a catalyst, and other optional components.
  • the above components may be mixed in any order. Any of the
  • composition additives for example fillers, may also be added to the composition during the mixing or prior to the mixing to form the composition.
  • the divinylarene dioxide, co-reactive curing agent, and optional components are admixed prior to addition of the curing catalyst.
  • All the components of the curable divinylarene dioxide resin composition are typically mixed and dispersed at a temperature enabling the preparation of an effective curable divinylarene dioxide resin composition having a low viscosity for the desired cation.
  • the temperature during the mixing of all components may be generally from about 0 °C to about 100 °C and preferably from about 20 °C to about 70 °C.
  • the excess divinylarene dioxide and co-reactive curing agent are mixed until homogeneously dispersed or dissolved prior to addition of optional components and catalyst.
  • the curable composition comprises a stoichiometric excess of a divinylarene dioxide, a co-reactive curing agent, and a catalyst, optionally including solvents and optional components as described above.
  • the curable composition of the present invention has a pot life increased over that of its stoichiometric analog of from about 10 % to about 10,000 %, preferably from about 20 % to about 5,000 %, and most preferably from about 50 % to about 1,000 %.
  • thermoset The curable composition of the present invention can be cured under conventional processing conditions to form a thermoset.
  • the resulting thermoset displays excellent thermo-mechanical properties, such as good toughness and mechanical strength, while maintaining high thermal stability.
  • thermoset products of the present invention may be performed by gravity casting, vacuum casting, automatic pressure gelation (APG), vacuum pressure gelation (VPG), infusion, filament winding, lay up injection, transfer molding, prepreging, dipping, coating, spraying, brushing, and the like.
  • APG automatic pressure gelation
  • VPG vacuum pressure gelation
  • the curing reaction conditions include, for example, carrying out the curing reaction under a temperature, generally in the range of from about 40 °C to about 300 °C; preferably, from about 50 °C to about 275 °C; and more preferably, from about 60 °C to about 250 °C.
  • the pressure of the curing reaction may be carried out, for example, at a pressure of from about 0.01 bar to about 1000 bar; preferably, from about 0.1 bar to about 100 bar; and more preferably, from about 0.5 bar to about 10 bar.
  • the curing of the curable composition may be carried out, for example, for a predetermined period of time sufficient to partially cure or to completely cure the composition.
  • the curing time may be chosen between about 1 minute to about 24 hours, preferably between about 10 minutes to about 12 hours, and more preferably between about 100 minutes to about 8 hours.
  • the curing process of the present invention may be a batch or a continuous process.
  • the reactor used in the process may be any reactor and ancillary equipment well known to those skilled in the art.
  • the cured or thermoset product prepared by curing the curable divinylarene dioxide resin composition of the present invention advantageously exhibits an improved balance of thermo-mechanical properties (e.g. glass transition temperature, modulus, and toughness.
  • the curable divinylarene dioxide resin composition of the present invention when cured, is capable of providing a thermoset or cured product wherein the heat resistance of the thermoset ranges generally from about 25 °C to about 300 °C; preferably, from about 50 °C to about 275 °C; and more preferably, from about 100 °C to about 250 °C as measured by the glass transition temperature (T g ) using differential scanning calorimetry (DSC).
  • T g glass transition temperature
  • the curable compositions of the present invention have a T g increased over that of its stoichiometric analog from about 5 % to about 100 %, preferably of about 5 % to about 75 %, and most preferably from about 10 % to about 50 %.
  • curable divinylarene dioxide resin compositions of the present invention are useful for the preparation of epoxy thermosets or cured products in the form of coatings, films, adhesives, laminates, composites, electronics, and the like.
  • the curable divinylarene dioxide resin compositions may be useful for casting, potting, encapsulation, molding, and tooling.
  • the present invention is particularly suitable for all types of electrical casting, potting, and encapsulation applications; for molding and plastic tooling; and for the fabrication of divinylarene dioxide resin based composites parts, particularly for producing large epoxy resin-based parts produced by casting, potting and encapsulation.
  • the resulting composite material may be useful in some applications, such as electrical casting applications or electronic encapsulations, castings, moldings, potting, encapsulations, injection, resin transfer moldings, composites, coatings and the like.
  • T g by DSC was obtained after curing using the cure schedules described below.
  • the curing catalyst was l-benzyl-2-methylimidazole (1B2MZ) at 2 wt % of the composition.
  • DVBDO and Rezicure 3000 were combined and heated to 75 °C with stirring to dissolve the phenolic resin. Then the catalyst was added and the mixture was stirred for 1 minute. The resulting composition was placed in an Al dish and cured in a recirculating air oven for 1 hour at 200 °C.
  • BPN was melted at ⁇ 130 °C with stirring and allowed to cool to 100 °C upon which DVBDO was added. The mixture was stirred until homogeneous. Then the catalyst was added and the mixture was stirred for 1 minute. The resulting composition was placed in an Al dish and cured in a recirculating air oven for 2 hours at 200 °C.
  • CHTP was melted at ⁇ 160 °C with stirring and allowed to cool to 120 °C upon which DVBDO was added. The mixture was stirred until homogeneous. Then the catalyst was added and the mixture was stirred for 1 minute. The resulting composition was placed in an Al dish and cured in a recirculating air oven for 2 hours at 250 °C.
  • Comparative Example D the composition solidified prior to addition of the curing catalyst and was not further tested.
  • Table II the ratio of epoxide/phenolic equivalents is "r.”
  • plaques weighing about 400 g and 200 mm X 300 mm X 4 mm in size are prepared by curing DVBDO with Rezicure 3000 in the presence of 1B2MZ catalyst at 80 °C for 60 min., then at 100 °C for 30 min., and finally at 200 °C for 60 minutes in a mold. Coefficients of thermal expansion were determined in the glassy (CTE g ) and rubbery (CTE r ) regimes using thermomechanical analysis in accordance to ASTM D 696.
  • T ⁇ j Thermal decomposition temperature
  • % residue after heating to 600 °C both under N 2
  • T ⁇ j Thermal decomposition temperature
  • % residue after heating to 600 °C both under N 2
  • E Tensile modulus
  • Kic fracture toughness
  • DVBDO-MTHPA thermosets Plaques of DVBDO-MTHPA thermosets were prepared using the mold as described above.
  • epoxy-anhydride thermosets the stoichiometric balance is defined using the mole ratios of epoxy resin/anhydride (m).
  • the molecular weights of DVBDO and MTHPA (this commercial grade) are 162 and 164 g/mole, respectively.
  • m 1 (balanced stoichiometry) and 177.0 g DVBDO, 166.6 g MTHPA, and 6.9 g 2-ethyl-4-methylimidazole (2E4MZ) catalyst were used.
  • thermosets Specimens of DVBDO-Jeffamine D-230 thermosets were prepared by curing formulations in an aluminum dish.
  • the equivalent weights of DVBDO and Jeffamine D-230 polyetheramine are 81 g/mole and 115 g/mole, respectively.
  • r 1 (balanced stoichiometry) and 2.0 g DVBDO and 1.5 g D-230 was cured for 1 hour each at 100 °C, 120 °C, 140 °C, and 150 °C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention a pour objet une composition de résine de dioxyde de divinylarène durcissable ayant un excès stœchiométrique de dioxydes de divinylarène durcie avec des amines, des anhydrides, ou des polyphénols. La composition de résine de dioxyde de divinylarène durcissable comprend (a) un excès stœchiométrique d'au moins un dioxyde de divinylarène, (b) un agent de durcissement co-réactif, et un catalyseur. La présente invention concerne également un procédé de fabrication de la composition de résine de dioxyde de divinylarène durcissable ci-dessus ; et une composition de résine de dioxyde de divinylarène durcie fabriquée à partir de celle-ci. La composition de résine de dioxyde de divinylarène durcissable possède une durée de vie en pot plus longue avant durcissement et produit un thermodurci ayant une résistance thermique plus élevée après durcissement que les compositions de l'art antérieur analogues fabriquées à l'aide de compositions stœchiométriques. Les compositions durcissables selon la présente invention sont avantageusement utiles en tant que matériaux, revêtements, composites, et adhésifs thermodurcis.
PCT/US2011/036945 2010-05-21 2011-05-18 Compositions durcissables WO2011146580A2 (fr)

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MX2012013529A MX2012013529A (es) 2010-05-21 2011-05-18 Composiciones curables.
BR112012029587A BR112012029587A2 (pt) 2010-05-21 2011-05-18 composição de resina epóxi contendo dióxido de divinilareno curável, processo para preparar uma composição de resina epóxi contendo dióxido de divinilareno curável, processo para preparar um termofixo curado e produto termofixo curado
US13/696,814 US20130059945A1 (en) 2010-05-21 2011-05-18 Curable compositions
CN2011800251447A CN102906148A (zh) 2010-05-21 2011-05-18 可固化组合物
RU2012155687/04A RU2581832C2 (ru) 2010-05-21 2011-05-18 Отверждаемые композиции
EP11721961A EP2571918A2 (fr) 2010-05-21 2011-05-18 Compositions durcissables
KR1020127033287A KR20130090789A (ko) 2010-05-21 2011-05-18 경화성 조성물
JP2013512081A JP2013533901A (ja) 2010-05-21 2011-05-18 硬化性組成物

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US61/347,074 2010-05-21

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WO2013043363A3 (fr) * 2011-09-21 2013-05-30 Dow Global Technologies Llc Compositions de résine à fonction époxy
WO2013188047A1 (fr) * 2012-06-15 2013-12-19 Dow Global Technologies Llc Durcisseur catalytique latent
WO2013188070A1 (fr) * 2012-06-15 2013-12-19 Dow Global Technologies Llc Compositions durcissables
WO2013188071A1 (fr) * 2012-06-15 2013-12-19 Dow Global Technologies Llc Catalyseur latent pour compositions durcissables
EP2861530A1 (fr) * 2012-06-15 2015-04-22 Dow Global Technologies LLC Compositions de carbone poreux
EP2861532A1 (fr) * 2012-06-15 2015-04-22 Dow Global Technologies LLC Composition de carbone vitreux
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US10335976B2 (en) * 2014-12-23 2019-07-02 Dow Global Technologies Llc Treated porous material
CN107057520A (zh) * 2017-02-15 2017-08-18 盘锦群益管道防腐有限公司 一种耐高温涂层的制备方法
CN114605355A (zh) * 2022-03-28 2022-06-10 国科广化(南雄)新材料研究院有限公司 一种二乙烯基芳烃二环氧化物及其固化产物的制备与应用

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JP2013533901A (ja) 2013-08-29
WO2011146580A3 (fr) 2012-04-05
EP2571918A2 (fr) 2013-03-27
KR20130090789A (ko) 2013-08-14
BR112012029587A2 (pt) 2016-08-02
WO2011146580A9 (fr) 2013-01-31
CN106008928A (zh) 2016-10-12
US20130059945A1 (en) 2013-03-07
CN102906148A (zh) 2013-01-30
RU2581832C2 (ru) 2016-04-20
MX2012013529A (es) 2013-01-24
TW201200535A (en) 2012-01-01

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